Yellow forming colour couplers for photographic silver halide material

ABSTRACT

1. PHOTOGRAPHIC COLOR MATERIAL COMPRISING IN A LIGHTSENSITIVE HALIDE EMULSION LAYER OR IN A NON-LIGHT-SENSITIVE WATER-PERMEABLE COLLOID LAYER IN WATER-PERMEABLE RELATIONSHIP WITH THE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AT LAST ONE COLOUR COUPLER CORRESPONDING TO THE FORMULA:   R1-O-(1,2-PHENYLENE)-CO-CH(-X)-CO-NH-(2-(R2-O-)-1,4-   PHENYLENE)-Y   WHEREIN: X REPRESENTS HYDROGEN, HALOGEN,-S-R&#39;&#39; AND -O-R&#34; WHEREIN R&#39;&#39; IS ALKYL, ARYL, OR HETEROCYCLE, AND R&#34; IS ALKYL, ARYL, OR ACYL, R1 AND R2 REPRESENT STRAIGHT-CHAIN OR BRANCHED-CHAIN ALKYL HAVING FROM 1 TO ABOUT 20 C-ATOMS, AND Y STANDS FOR COOR3,   -CO-N(-R4)-R5, -SO2-R6 OR -SO2-N(-R7)-R8   WHEREIN R3 AND R6 REPRESENT A STRAIGHT-CHAIN OR BRANCHED-CHAIN ALKYL GROUP OR AN ALKOXY ALKYL GROUP, AND R4, R5, R7 AND R8 REPRESENT HYDROGEN OR HAVE THE SAME SIGNIFICCANCE GIVEN FOR R3 AND R6, THE COLOR COUPLER MOLECULE COMPRISING AT LEAST ONE ALKYL GROUP RENDERING THE MOLECULE FAST TO DIFFUSION IN HYDROPHILIC COLLOID MEDIA.

United States Patent 3,843,366 YELLOW FORMING COLOUR COUPLERS FOR PHOTOGRAPHIC SILVER HALIDE MATERIAL Raphael Karel Van Poucke, Berchem, Gaston Jacob Benoy, Edegem, and Arthur Henri De Cat, Mortsel, Belgium, assignors to Agfa-Gevaert N.V., Mortsel, Belgium No Drawing. Filed Mar. 6, 1972, Ser. No. 232,185 Claims priority, application Germany, Mar. 25, 1971, P 21 14 578.8 Int. Cl. G03c 7/00, 1/40 US. Cl. 96-55 11 Claims ABSTRACT OF THE DISCLOSURE Novel benzoylacetanilide compounds are described which correspond to the formula:

wherein X represents hydrogen or a group that exhibits two-equivalent character on colour development,

R and R represent straight-chain or branched-chain alkyl having from 1 to about 20 C-atoms, and

Y stands for COOR wherein R and R represent a straight-chain or branched-chain alkyl group of which the carbon chain may be interrupted by oxygen, and R R R and R represent hydrogen or have the same significance given for R and R They are described for use as colour couplers in lightsensitive silver halide emulsions where, upon colour clevelopment, they yield dyes with excellent spectral characteristics and high stability.

This invention relates to the production of photographic colour images, to colour couplers for yellow used therein and to photographic materials containing such colour couplers.

It is known that for the production of a photographic colour image in a light-sensitive silver halide layer, the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a colour coupler which reacts with the oxidized developing substance to form a dyestuff on the areas corresponding to the silver image.

In the subtractive three-colour photography a light-sensitive photographic colour material is used containing a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on colour development, by use of appropriate colour couplers, a cyan, magenta and yellow dyestuff image are formed respectively.

Colour couplers for yellow of the benzoylacetarylide type having an o-alkoxy-substituent in the benzoyl part of the molecule generally yield upon colour development dyes having a higher stability than those containing in the benzoyl part a p-alkoxy substituent or no alkoxy substituent at all.

By the introduction of an o-alkoxy substituent in the anilide part of the molecule it is possible to realize a hypsochromic shift of the absorption maximum of the azornethine dyes formed on colour development. However, these compounds are found to have a low coupling activity and to yield upon colour development azomethine dyes with low extinction.

It is therefore an object of the present invention to provide novel benzoylacetanilide colour couplers for yellow having a high coupling activity i.e. colour couplers which furnish dye images with high maximum density and gradation.

Another object of the present invention is to provide colour couplers for yellow having favourable spectral properties i.e. colour couplers which produce upon colour development yellow azomethine dyes with very low sideabsorption in the green and red region of the spectrum.

A further object of the present invention is to provide colour couplers which produce upon colour development yellow azornethine dyes with hypsochromic absorption maxrma.

Other objects will become apparent from the description below and the examples hereinafter.

The above objects are accomplished by the use of novel benzoylacetanilide colour couplers corresponding to the following general formula:

coonxo ONHQ-Y wherein:

X represents a hydrogen atom or .a substituent that exhibits two equivalent character on colour development e.g. a halogen atom, an SR' group wherein R' is alkyl, substituted alkyl, aryl, substituted aryl, a heterocycle or a substituted heterocycle or an -OR" group wherein R represents alkyl, substituted alkyl, aryl, substituted aryl, acyl or substituted acyl, e.g. acetyl and benzoyl,

R and R represent a branched-chain or straight-chain alkyl having from 1 to about 20 C-atoms, and

Y represents COOR R4 R1 CON SOzRa 0! SOzN a Ra wherein R and R represent a straight chain or branched-chain alkyl group of which the carbon chain may be interrupted by oxygen, and R R R and R rep resent hydrogen or have the same significance given for R and R -COCH2CONH COOCH:

l -oocrnc ONE-@000 0111011 0011.

0 (CH2)15CH3 O CH:

-cocmooNn--cooom 4. on. 0 CH:

-oocmoonrr co o (CH2)15CH;

5. C(CH2)15CH3 00H:

Q00 CHzCONH-CO o 0112-0110111:

DHltl-i o. o (CHzhaCI-Is 0 on.

Q00 CHClCONH--CO 0 on. 7. ?(CH2)15CHa 0 CH3 Q00 CHzCONH-CO 0011201120 CH3 8. 0 CH3 0 (CH2)11CH3 @430 0320 ONHS 02cm 9. 0 (CHfiuCHa 0 CH3 oo omconn-Q-s 020m 10. 0 (CH mCH; 0 on.

Q-co cHo1ooNHs 02cm 11. 0 (CHZ)CH3 0 CH3 /CH3 ooomoomr- -s om CH: 12. 0 on. o (CHzhaCH:

/CH3 cocmooNH- SOzN CH; 13. O CH: O (CH2)15CH:!

Q00 CHCICONH-Q-CO 0 on.

14. 0 CH3 0 CH: @000....,.H ..N. .H.....H..0...

15: O (CH2)15CH3 0 CH3 COCHzCONH- CONH-C(CH3) The following preparations illustrate how the novel colour couplers according to the present invention can be prepared.

PREPARATION 1 Colour coupler 1 (a) 3-n-hexadecyloxy-4-nitro-benzoic acid methyl ester.--To a solution of 394 g. 3-hydroxy-4-nitrobenzoic acid methyl ester in 2.8 litres of acetone, a solution of 132 g. of potassium hydroxide in 230 ml. of methanol was added. The potassium salt formed was filtered off and washed with water. The nitrophenolate as well as 573 g. of hexadecyl bromide were placed in 1500 ml. of dimethylformamide and stirred for 2 hours at a temperature of 95 C. The reaction mixture was poured into 2.5 litres of water at 80 C. The mixture was cooled to room temperature and the precipitate was filtered oil and washed with methanol. Yield: 663 g. Melting point: 66 C.

(b) 3-n-hexadecyl0xy-4-amino-benzoic acid methyl ester.661 g. of the above nitro compound was dissolved in 3 litres of ethanol and hydrogenated at 80 C. and a hydrogen pressure of 1500 p.s.i. using 50 g. of Raney nickel as catalyst. The catalyst was filtered off and the solution was cooled to room-temperature. The precipitate formed was filtered off. Yield: 526 g. Melting point: 78- 80" C.

(c) Colour coupler l.117.3 g. of 3-n-hexadecyloxy- 4-aminobenzoic acid methyl ester and 62.4 g. of o-methoxybenzoylacetic acid methyl ester were boiled in 230 ml. of xylene. For 2 hours the methanol formed was distilled off and the xylene was then removed by evaporation under reduced pressure. The residue was boiled with methanol and the precipitate formed was recrystallized from n-hexane. Yield: 109 g. Melting point: 74 C.

PREPARATION 2 Colour coupler 2 (a) 3-n-hexadecyloxy-4-nitrobenzoic acid Z-methoxy ethyl ester.To a solution of 10 g. of sodium in 2 litres of ethylene glycol monomethyl ether, 745 g. of 3-n-hexadecyloxy-4-nitrobenzoic acid methyl ester were added. The mixture was refluxed for 3 hours, poured into 3 litres of water and then acidified by addition of acetic acid. The precipitate formed was filtered off, dried in vacuum and recrystallized from acetonitrile. Yield: 361 g. Melting point: 38 C.

(b) 3-n-hexadecyloxy-4-aminobenzoic acid Z-methoxyethyl ester.The above nitro compound was dissolved in ethylene glycol monomethyl ether and hydrogenated at C. under a hydrogen pressure of 1500 p.s.i. using Raney nickel as catalyst.

Melting point: 72 C.

(c) Colour coupler 2.--This compound was prepared in a similar way as colour coupler 1. Yield: 80 C.

PREPARATION 3 Colour coupler 3 (a) 3-methoxy-4-nitrobenzoic acid methyl ester.-70O g. of the potassium salt of 3-hydroxy-4-nitrobenzoic acid methyl ester were stirred in 3 litres of dimethyl formamide whereupon 420 ml. of dimethyl sulphate were added at 70 C. The mixture was heated for 45 min. on a water-bath of C. and then poured into 5 litres of water. The precipitate formed was filtered off and washed with water. Yield: 606 g. Melting point: 90 C.

(b) 3-methoxy-4-aminobenzoic acid methyl ester.400 g. of the above nitro compound were dissolved in 3 litres of methanol and then hydrogenated at 60 C. under a hydrogen pressure of 1500 p.s.i. using Raney nickel as catalyst. Yield: 280 g. Melting point: C.

(c) Colour coupler 3.-This compound was prepared by condensation of 3-methoxy-4-aminobenzoic acid methyl ester and o-n-hexadecyloxybenzoic acid methyl ester, prepared as described in British Patent Application No. 854/68 according to the method of preparation 1. Melting point: 76 C.

PREPARATION 4 Colour coupler 4 (a) 3 methoxy 4 aminobenzoic acid n-hexadecyl esterl80 g. of 3-methoxy-4-aminobenzoic acid methyl ester and 363 g. of hexadecyl alcohol were heated at C. in the presence of 2.5 ml. of titanium tetrabutoxide as catalyst. Nitrogen was introduced into the melt and in the course of 3 hours 38 ml. of methanol were distilled off. The mixture was cooled to 70 C. and then treated with methanol. The precipitate formed was filtered off and dried. Yield: 366 g. Melting point: 72 C.

(b) Colour coupler 4.This colour coupler was prepared by condensation of o-methoxy-benzoyl acetic acid ethyl ester and 3-methoxy-4-aminobenzoic acid n-hexa-- decyl ester according to the method of preparation 1. Recrystallization occurred from cyclohexane. Melting point: 86 C.

PREPARATION 5 Colour coupler 5 (a) 3 methoxy-4-aminobenzoic acid isooctadecyl ester.-This compound, which was obtained in the form of an oil, was prepared in a similar Way as the com-.

pound of preparation (4a) from 3-methoxy'4-aminobenzoic acid methyl ester and isooctadecyl alcohol (commercially available e.g. from Farbwerke Hoechst A.G., Frankfurt (M), Hochst, W. Germany).

(b) By condensation of 3-methoxy-4-aminobenzoic acid isooctadecyl ester with o-n-hexadecyloxybenzoic acid methyl ester according to the procedure of preparation 1, an oil was obtained.

100 g. of the oil were dissolved in 75 ml. of ethanol and the solution was treated with a solution of 35 g. of copper acetate in 175 ml. of water. The precipitate formed was washed with water and ethanol, then dissolved in 250 ml. of methylene chloride and agitated with 120 ml. of 5N hydrochloric acid. The organic layer was washed with water till neutral and then dried over magnesium sulphate. After evaporation of the methylene chloride 100 g. are obtained with an active methylene content of 98% PREPARATION 6 Colour coupler 6 By condensation of o-tetradecyloxybenzoyl acetic acid methyl ester with 3-methoxy-4-amino-benzoic acid methyl ester a colour coupler was obtained which, after recrystallization from acetonitrile, had a melting point of 76 C.

54 g. of this colour coupler were dissolved in 250 ml. of chloroform and then treated with a solution of 8.1 ml. of sulphuryl chloride in 50 ml. of chloroform. After 50 min. the solvent was removed by evaporation under reduced pressure and the residue was recrystallized from acetonitrile. Melting point: 84 C.

PREPARATION 7 Colour coupler 7 (a) 3-methoxy-4-amino-benzoic acid fi-methoxyethyl ester.--108 g. of 3-methoxy-4-amino-benzoic acid methyl ester, 150 ml. of ethylene glycol monomethyl ether and 2.5 ml. of titanium tetrabutoxide were boiled for 16 hours while introducing nitrogen and distilling off the methanol formed. The excess of alcohol was removed and the residue recrystallized from n-hexane. Melting point: 60 C.

(b) Colour coupler 7.-167 g. of o-hcxadecyloxybenzoylacetic acid methyl ester were condensed with 90 g. of the above amine in 300 ml. of xylene. In 90 min. 14 ml. of methanol were distilled off. The mixture was concentrated by evaporation under reduced pressure and the residue was recrystalized from isopropyl ether. Yield: 160 g. Melting point: 68 C.

PREPARATION 8 Colour coupler 8 (a) 2-dodecyloxy-4-thiocyanato aniline.-To 55.4 g. of 2-dodecyloxyaniline and 30.4 g. of ammonium thiocyanate in 200 ml. of acetonitrile, 10.3 g. of bromine were added in 30 min. with stirring at a temperature above 23 C. The reaction mixture was poured into water and neutralized by means of 1N sodium hydroxide. The crystals formed were extracted with methylene chloride and after drying over magnesium sulphate, the methylene chloride was removed. Melting point: 40 C.

(b) 2-dodecyloxy-4-thiocyanato acetanilide-33.4 g. of 2-dodecyloxy-4-thiocyanatoaniline were dissolved in 60 ml. of acetic acid and 100 ml. of water. After addition of 12 ml. of acetic anhydride the mixture was left standing overnight at room temperature. The precipitate formed was filtered ofl, dried and recrystallized from n-hexane. Melting point: 58 C.

(c) 2-dodecyloxy-4-methylthio-acetanilide.--To 37.6 g. of the above acetanilide and 14.2 g. of methyl iodide in 75 ml. of methanol a solution of 4.6 g. of sodium in 75 ml. of methanol was added. The mixture was refluxed for 3 hours and the precipitate formed was filtered off and washed with water. Yield: 32.2 g. Melting point: 73 C.

(d) 2-dodecyloxy-4-methylsulph-onyl aniline.36.5 g. of 2-dodecyloxy-4-methylthioacetanilide were dissolved in 50 ml. of acetic acid and heated till the mixture began to reflux. Then 56.4 g. of urea peroxide were slowly added. When the exothermic reaction ceased, the mixture was cooled to room temperature and the precipitate formed was filtered off. The product was recrystallized from isopropyl ether. Melting point: 98 C.

The acetanilide was hydrolyzed in 50 ml. of 5N hydrochloric acid and 50 ml. of ethanol. After having refluxed the reaction mixture for 2 hours it was neutralized by addition of ammonium hydroxide. The precipitate formed was filtered OH and recrystallized from methanol. Melting point: 74 C.

(e) Colour coupler 8.53.2 g. of 2-dodecyloxy-4-methylsulphonylaniline and 31.2 g. of o-methoxybenzoylacetic acid methyl ester were condensed in 112 ml. of xylene. The methanol was removed by evaporation and the xylene was removed by evaporation under reduced pressure. The residue was recrystallized from methanol. Melting point: 65 C.

PREPARATION 9 Colour coupler 9 (a) 2-methoxy-4-thiocyanatoacetanilide.900 g. of 2- methoxy-4-thiocyanatoaniline, prepared according to R. Pohloudek-Fabini, Arch. Pharmazie 299 (10) 866877 (1960), in 3 litres of acetic acid and 3 litres of water were acetylized by means of 600 ml. of acetic anhydride at a temperature of 30 C. Yield: 747 g. Melting point: 136 C.

(b) 2-methoxy-4-methylthio-acet:anilide.-To 444 g. of 2-methoxy-4-thiocyanato-acetanilide and 284 g. of methyl iodide in 2 litres of methanol, a solution of 92 g. of sodium in 1.5 litres of methanol was added at a temperature of 45 C. The mixture was refluxed for 4 hours and then poured into water. The precipitate formed was extracted with methylene chloride and after removal of the extracting solvent the residue was recrystallized from hexanebenzene (60:40). Melting point: 96 C.

(c) 2-methoxy-4-methylsulphony1 aniline.-21l g. of 2- methoxy-4-methylthioacetanilide were dissolved in 200 ml. of acetic acid and the solution was heated to C. Then 282 g. of urea peroxide dissolved in 1300 ml. of acetic acid was added. When the reaction ceased, water was added and the precipitate formed was filtered off.

The precipitate Was boiled for 2 hours in 400 ml. of ethanol and 480 ml. of 5N hydrochloric acid whereupon the mixture was neutralized by addition of ammonium hydroxide. The precipitate was filtered otf, dried and recrystallized from acetonitrile. Melting point: 135 C.

(d) Colour coupler 9.100 g. of 2-methoxy-4-methylsulphonyl aniline and 209 g. of o-hexadecyloxybenzoyl acetic acid ethyl ester were condensed in 325 ml. of xylene. The methanol formed was removed by evaporation and the xylene was evaporated under reduced pressure. The residue was recrystallized from methanol. Yield: 220 g. Melting point: 113 C.

PREPARATION 10 Colour coupler 10 To a solution of 117 g. of colour coupler 9 in 500 ml. of chloroform, a solution of 16.2 m1. of sulphuryl chloride in 100 ml. of chloroform was added. The mixture was stirred for 1 hour at room temperature whereupon the precipitate was filtered off and recrystallized from cyclohexane. Melting point: 100 C.

PREPARATION 11 Colour coupler 11 (a) 6-N,N-dimethylaminobenzoxazolone-2.-187 g. of 6-chlorosulphonyl-benzoxazolone-Z, prepared as described in J. Am. Chem. Soc. 63, 879 (1941), were dissolved in 1.5 litres of dioxan whereupon gaseous dimethylamine was introduced with stirring whereby the temperature rose to 53 C. The mixture was cooled to room temperature and then poured into 3 litres of water. The precipitate formed was filtered off and dried. Yield: 137 g. Melting point: 202 C.

(b) 2-amino-5-N,N-dimethylaminosulphonylphenol.-- 141 g. of 6-N,N-dimethylaminobenzoxazolone-2 in 300 ml. of N sodium hydroxide were boiled for 4 hours whereupon 300 ml. of water were added and the mixture was neutralized by addition of 2N hydrochloric acid. The precipitate was filtered off and recrystallized from ethanol. Yield: 105 g. Melting point: 184 C.

(c) 2-acylamino 5 N,N dimethylaminosulphonylphen0l.--43.2 g. of the above amine were dissolved in 200 ml. of 4% sodium hydroxide whereupon 24.6 g. of acetic anhydride were added with stirring. The mixture was stirred for min. and then neutralized by means of hydrochloric acid. The precipitate formed was filtered off. Yield: 28 g. Melting point: 245 C.

(d) 2-amnio-5-N,N dimethylaminosulphonylanisol.- 26 g. of the above acylaminophenol compound were dissolved in a solution of 6.6 g. of potassium hydroxide in 40 ml. of methanol. After addition of 6.2 ml. of methyl iodide the mixture was refluxed for min. and then poured into water. The precipitate formed was recrystallized from acetonitrile. Melting point: 190 C.

27.2 g. of the product and 77 ml. of 6N hydrochloric acid were refluxed for 1 hour in ethanol. The mixture was poured into water and neutralized by addition of ammonium hydroxide. The precipitate was filtered off and recrystallized from ethanol. Yield: 18 g. Melting point: 150 C.

(e) Colour coupler 11.124.5 g. of o-hexadecyloxybenzoylacetic acid methyl ester and 57.5 g. of 2-amino-5- N,N-dimethylaminosulphonylanisol were condensed in 190 ml. of xylene. In 90 min. 45 ml. of solvent were distilled 01f. The mixture was cooled and methanol was added. The precipitate formed was filtered off and recrystallized from ethyl acetate. Yield: 113 g. Melting point: 88 C.

PREPARATION 12 Colour coupler 12 (a) 2-n-hexadecyloxy-4-N,N-dimethylaminosulphonylacetanilide.-206 g. of 2-acylamino 5 N,N dimethylaminosulphonylphenol were dissolved in 640 ml. of ethylene glycol monomethyl ether into which 18.4 g. of sodium was dissolved. 244 g. of hexadecyl bromide were added and the mixture was refluxed for 1 hour whereupon it was poured into water. The precipitate was filtered off and recrystallized from ethanol. Yield: 312 g. Melting point: 96 C.

(b) 2-n-hexadecyloxy-4-N,N-dimethylaminosulphonylaniline.-96.4 g. of the above acetanilide and 150 ml. of 5N hydrochloric acid were refluxed in ethanol for 1 hour. The solution was neutralized by addition of ammonium hydroxide whereupon the precipitate formed was filtered off, washed with water and recrystallized from ethanol. Yield: 80 g. Melting point: 92 C.

(c) Colour coupler 12.-31.2 g. of o-methoxybenzoylacetic acid methyl ester and 66 g. of 2-n-hexadecyloxy-4- N,N-dimethylaminosulphonylaniline in 120 ml. of xylene were heated to the boiling point and 50 ml. of solvent were distilled off in 90 min. The mixture was cooled whereupon methanol was added and the precipitate formed was filtered oil. The product was recrystallized from ethyl acetate. Melting point: 103 C.

The yellow colour formers according to the present invention are of the non-diffusible type; they comprise in their molecule at least one acyclic aliphatic hydrocarbon group sufficiently large for preventing the colour coupler of wandering from the colloid layer, in which the coupler is incorporated, to another colloid layer.

For preparing a usable photographic multilayer colour material the non-diffusion colour couplers for each colour separation image are usually incorporated into the coating compositions of the differently sensitized silver halide emulsion layers. However, the non-diffusing colour couplers may also be added to the coating compositions of non-light-sensitive colloid layers which are in water-permeable relationship with the light-sensitive silver halide emulsion layers e.g. in layers which are in direct contact with the light-sensitive layers or which are separated from said light-sensitive layers by Water-permeable non-lightsensitive layers.

During the preparation of the light-sensitive colour material the non-migratory yellow forming colour couplers according to the above general formulae can be incorporated in the coating composition of the silver halide emulsion layers or other colloid layers in waterpermeable relationship therewith according to any technique known by those skilled in the art for incorporating water-insoluble photographic ingredients, more particularly water-insoluble colour couplers, into colloid compositions. For instance, the colour couplers can be incorporated into the coating composition of the layer in question from a solution in the appropriate water-miscible or water-immiscibel high-boiling or low-boiling organic solvent or mixture of these solvents whereupon the solution obtained is dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophilic colloid composftion forming or forming part of the binding agent of the colloid layer. The hydrophilic colloid composition may of course comprise in addition to the colloid carrier all other sorts of ingredients.

The solution of said colour coupler need not necessarily be dispersed directly in the coating composition of the silver halide emulsion layer or other water-permeable layer. Said solution may advantageously be first dispersed or dissolved in an aqueous non-light-sensitive hydrophilic colloid solution whereupon the resultant mixture, after the removal (if necessary) of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.

For more details about particularly suitable dispersing techniques that may be employed for incorporating the colour couplers of the invention into a hydrophilic colloid layer of a photographic material there can be referred to e.g. United States Patent Specifications 2,269,158, 2,304,- 939, 2,304,940 and 2,322,027, United Kingdom Patent Specifications 791,219, 1,098,594, 1,099,414, 1,099,415, 1,099,416 and 1,099,417, French Patent Specification 1,555,663, German Patent Specification 1,127,714 and to United Kingdom Patent Applications 14,763/69, 39,115/ and 39,116/70.

The colour couplers of the invention are preferably incorporated into hydrophilic colloid media from solutions in high-boiling sparingly water-miscible solvents such as di-n-butyl phthalate and tricresyl phosphate or in low-boiling sparingly water-miscible solvents such as ethyl acetate, methylene cholride, chloroform, etc. or mixtures thereof in that they have a high solubility therein and very fine dispersions in hydrophilic colloid compositions of the colour couplers of the invention can be obtained by means of these solvents. For this purpose these solutions are dispersed in extremely fine droplets in the presence of a wetting or dispersing agent into the hydrophilic colloid medium the low-boiling sparingly water-miscible solvent then being removed by evaporation.

The couplers according to the invention may be used in conjunction with various kinds of photographic emulsions. Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide. The couplers can be used in emulsions of the mixed packet type as described in United States Patent Specification 2,698,794 or emulsions of the mixed grain type as described in United States Patent Specifictaion 2,592,243. The colour couplers can be used with emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.

The hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, etc. If desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.

The light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Patent Specification 1,146,- 955 and in Belgian Patent Specification 568,687, iminoamino methane sulphinic acid compounds as described in United Kingdom Patent Specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds. They may be optically sensitized by means of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize the emulsions by development acceleration for example compounds of the polyoxyalkylene type such a as alkylene oxide condensation products as described among others in United States Patent Specifications 2,531,832, 2,533,990, 3,210,191 and 3,158,484, in United Kingdom Patent Specifications 920,637, and 991,608 and in Belgian Patent Specification 648,710 and onium derivatives of amino-N-oxides as described in Untied Kingdom Patent Specification 1,121,696.

Further, the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121, 677,337 and 707,- 386 and in United States Patent Specification 3,179,520.

The light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.

The non-diifusing yellow colour formers described in the present invention are usually incorporated into the blue-sensitive silver halide emulsion for forming one of the differently sensitized silver halide emulsion layers of a photographic multilayer colour material. Such photographic multilayer colour material usually comprises a support, a red-sensitized silver halide emulsio layer with a cyan colour former, a green-sensitized silver halide emulsion layer with a magenta colour former and a bluesensitive silver halide emulsion layer with a yellow colour former.

The emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials, as well as paper and glass.

For the production of photographic colour images according to the present invention an exposed silver halide emulsion layer is developed with an aromatic primary amino developing substance in the presence of a colour coupler according to the present invention. All colour developing agents capable of forming azomethine dyes can be utilized as developers. Suitable developing agents are aromatic primary amino compounds for example N,N-dialkylp-phenylene diamines and derivatives thereof e.g. the toluene analogues. Typical examples of aromatic primary amino colour developing agents are: N,N-diethylp-phenylene diamine, Z-amino-5-diethylaminotoluene, N-

10 butyl-N-sulphobutyl-p-phenylene diamine 2-amino-5-[N- ethyl N( fi-methylsulphonamido ethyl] aminotoluene, N ethyl-N-fl-hydroxyethyl-p-phenylene diamine etc. These developing agents are usually used in their salt form such as the hydrochloride or sulphate.

The yellow colour formers according to the invention form on colour development yellow azomethine dyes which excell by their favourable light absorption in the blue region of the spectrum and little absorption in the other regions of the spectrum. Furthermore, the colour couplers manifest a high activity during development i.e., they furnish colour images with high colour density.

In order to prove the favourable characteristics of the yellow forming colour couplers of the present invention comparative tests were carried out as set forth in the following examples.

Example 1 0 (CH2) E:

-o 0 onto ONH-Q-C o 0 Q2115 was added per kg. The latter colour coupler has a melting point of 71 C. and was prepared in a similar way as the colour couplers of the invention by condensation of 104.5 g. of o-hexadecyloxybenzoylacetic acid methyl ester and 41 g. of p-aminobenzoic acid ethyl ester in 190 ml. of xylene.

After addition of the common additives such as stabilizers, wetting agents and hardeners the emulsions were coated on a film support pro rata of g. per sq. m. The emulsion layers were dried and overcoated with a gelatin antistress layer.

After drying, the materials formed were exposed for V sec. through a continuous wedge and developed for 10 min. at 24 C. in a developing bath of the following composition:

G. Sodium hexametaphosphate 2 Anhydrous sodium sulphite 4 Anhydrous sodium carbonate 17 Potassium bromide 2 2-amino-5-diethylaminotoluene hydrochloride 3 Water to make 1 litre.

The developed materials were treated for 5 min. at 24 C. in a fixing bath of the following composition:

Water ml 800 Anhydrous sodium thiosulphate g 200 Potassium metabisulphite g 12 Glacial acetic acid ml 12 Borax g 20 Potassium alum g 15 Water to make mL.. 1000 The materials were rinsed for 15 min. with water and then treated for 8 min. at 20 C. in a bleach bath of the following composition:

Potassium bromide g 20 Potassium bichromate g 5 Potassium alum g- 40 Water to make rnl 1000 After bleaching, the materials were rinsed with Water for 5 min. 'and fixed for 5 min. at 24 C. in the above fixing solution.

After a final rinsing for 10 min. the materials were dried.

Yellow coloured wedge images were obtained showing the following sensitometric results.

Relative Gra- Maximum Emulsion speed dation density A 100 l. 04 1. 98 B 32 0. 78 1. 34

Absorp- Percentage absorption tion maximum Emulsion (nm.) Blue Green Red Moreover, the yellow dye image formed in accordance with the present invention shows good resistance to heat and humidity.

' Example 2 Two emulsions are prepared as described in Example 1. Emulsion A contains per kg. 0.006 mole of colour coupler 1 and emulsion B contains per kg. 0.006 mole of the colour coupler with formula:

mo o-c 0 011010 ONE-Q which was prepared as follows:

66.6 g. of p-methoxybenzoylacetic acid ethyl ester and 117 g. of 3-hexadecyloxy-4-aminobenzoic acid methyl ester were condensed in xylene to yield 113.5 g. of product melting at 118 C. after recrystallization from ethyl acetate. 57 g. of the product were dissolved in chloroform and treated with 8.1 ml. of sulphuryl chloride. The product was recrystallized from methanol. Yield: 56 g. Melting point: 87 C.

After exposure and processing as described in Example 1 yellow wedge images are obtained. As can be learned from the results listed in the table below the colour couplers with o-alkoxy group in the benzoyl part of the molecule give rise to less fog than the corresponding colour couplers with an alkoxy group in the p-position of the benzoyl part of the molecule. Moreover, as compared with the yellow dye image obtained in emulsion B, the yellow dye image obtained in emulsion A has a hypsochrome absorption maximum.

-COOCH3 Absorp- Fog in tion maximum Emulsion Blue Green Red (nm.)

Example 3 This example is analogous to Example 2 with the difference that processing occurs as follows.

1. Development for 8 min. at C. in a developing bath of the following composition:

Water to make 1 litre.

2. Treatment for 2 min. at 1820 C. in an intermedi ate bath comprising 30 g. of sodium sulphate in 1 litre of water.

3. Rinsing for 15 min. with water.

4. Treatment in a bleach bath of the following composition:

G. Borax 20 Anhydrous potassium bromide 15 Anhydrous sodium bisulphate 4.2 Potassium hexacyanoferrate(III) Water to make 1 litre.

5. Rinsing with water for 5 min.

6. Fixing in an aqueous solution of 200 g. of sodium thiosulphate per litre.

7. Final rinsing for 15 min.

The following results were obtained.

To a gelatino silver bromoiodide emulsion as described in Example 1, 0.006 mole of colour coupler 2 was added per kg.

After addition of the common additives such as stabilizers, wetting agents and hardeners the emulsion was coated on a film support pro rata of g. per sq. m. The emulsion layer was dried and overcoated with a gelatin antistress layer.

After drying, the material was exposed to see. through a continuous wedge and developed for 15 min. at 21 C. in a developing bath of the following composition:

Sodium hexametaphosphate g 2 Anhydrous sodium sulphite g 2 Benzyl alcohol ml 3.8 10% aqueous sodium hydroxide ml 5.5 Sodium carbonate monohydrate g 50 Potassium bromide g 0.85 2 amino-5-[N-ethyl-N(fi-methylsulphonyl-amino) ethyl] aminotoluene sulphate g 5 Water to make ml 1000 The developed material was treated for 5 min. at 21 C. in the fixing bath of Example 1, rinsed for 10 min. with water and then treated for 7 min. at 21 C. in the bleach bath of Example 1.

After bleaching the material was rinsed with water for 5 min. and fixed for 5 min. at 21 C. in the same fixing solution.

After a final rinsing for 10 min. the material was dried.

A yellow coloured wedge image was obtained the absorption maximum of which is at 436 nm.

When using instead of colour coupler 2, 0.006 mole of the colour coupler corresponding to the formula:

0 (CH2) i5CHa HaCO- COOHzCONH- COOCHzCHzOCH Example 5 Examples 1, 3 and 4 were repeated with the difference that colour coupler 3 was used as colour coupler according to the present invention and the colour coupler corresponding to the formula below was used as comparison colour coupler:

O (CH2)15CH3 CH3 C O CHzC ONH- IOOCHa From the values of the gradation and maximum density obtained after exposure and processing as described in Examples 1, 3 and 4 above which values are listed in the table below it is clearly apparent that the colour couplers of the invention have a high coupling activity which is higher than that of the corresponding structurally isomeric colour couplers carrying a substituent in the -position of the anilide group rather than in the 4-position.

TABLE Processing of Example 1 Example 3 Example 4 Colour coupler used- '7 max- 7 umb 'y ina!- Colour coupler 3 0. 83 1. 65 0.63 1. 63 0.77 1. 55 Comparison colour coupler 0.51 1. 27 0. 49 1. 29 0.61 l. 23

water-permeable colloid layer in water-permeable relation- 3 ship with the light-sensitive silver halide emulsion layer at least one colour coupler corresponding to the formula:

wherein:

X represents hydrogen, halogen, S-R and O-R" wherein R is alkyl, aryl, or heterocycle, and R" is alkyl, aryl, or acyl,

R and R represent straight-chain or branched-chain alkyl having from 1 to about 20 C-atoms, and

Y stands for COOR R4 CON 30 m or SO N wherein R and R represent a straight-chain or branched-chain alkyl group or an alkoxy alkyl group, and R R R and R represent hydrogen or have the same significance given for R and R the colour coupler molecule comprising at least one alkyl group rendering the molecule fast to diffusion in hydrophilic colloid media.

2. Photographic colour material according to claim 1 wherein the said material is a multilayer colour material comprising three silver halide emulsion layers which have a different spectral sensitivity, including a blue-sensitive silver halide emulsion layer, the said blue-sensitive silver halide layer or a non-light-sensitive water permeable colloid layer adjacent thereto incorporating the said colour coupler(s).

3. Process for the production of a photographic colour image by development of a photographic element containing imagewise exposed silver halide with the aid of a developing agent, which by reduction of the exposed silver halide is converted into its oxidized form and as such forms a yellow azomethine dye by reaction with at least one colour coupler corresponding to the formula:

wherein:

X represents hydrogen, halogen, -SR' and -OR" wherein R is alkyl, aryl, or heterocycle, and R" is alkyl, aryl, or acyl,

R and R represent straight-chain or branched-chain alkyl having from 1 to about 20 C-atoms, and

Y stands for COOR wherein R and R represent a straight-chain or branched-chain alkyl group or an alkoxy alkyl group, and R R R and R represent hydrogen or have the same significance given for R and R the said colour coupler(s) being present in a blue-sensitive silver halide emulsion layer or other colloid layer in water-permeable relationship therewith of the said photographic element.

4. The photographic color material of claim 2 wherein X is hydrogen.

5. The photographic color material of claim 2 wherein X is halogen.

6. The photographic color material of claim 2 wherein X is SR wherein R is alkyl or aryl.

7. The photographic color material of claim 2 wherein X is O-R" wherein R" is alkyl, aryl, or acyl.

8. The process of claim 3 wherein X is hydrogen. 9. The process of claim 3 wherein X is halogen. 10. The process of claim 3 wherein X is S-R wherein R is alkyl or aryl.

11. The process of claim 3 wherein X is O-R" wherein R is alkyl, aryl, or acyl.

References Cited UNITED STATES PATENTS 2,407,210 9/1946 Weissberger et al 96-400 3,409,439 11/1968 Yoshida et al. 96-l00 3,725,072 4/1973 Yoshida et al. 96100 1. TRAVIS BROWN, Primary Examiner US. Cl. XR. 

1. PHOTOGRAPHIC COLOR MATERIAL COMPRISING IN A LIGHTSENSITIVE HALIDE EMULSION LAYER OR IN A NON-LIGHT-SENSITIVE WATER-PERMEABLE COLLOID LAYER IN WATER-PERMEABLE RELATIONSHIP WITH THE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AT LAST ONE COLOUR COUPLER CORRESPONDING TO THE FORMULA: 